Post on 24-Jun-2020
X-RAY TRANSIENT ABSORPTION SPECTROSCOPY
Lin X. Chen
Chemical Sciences and Engineering Division, Argonne National Laboratory
Department of Chemistry, Northwestern University
August 7-12, 2017
19th National School on Neutron and X-ray Scattering Summer School
X-ray Transient Absorption Spectroscopy
Taking Snapshots of Photoexcited Molecular Structures in Disordered Media Using Pulsed X-rays, Lin X. Chen, Angew. Chemie. Intl. Ed., 43, 2886-2905 (2004). Ultrafast X-ray absorption spectroscopy, C. Bressler and M. Chergui, Chem Rev. (2004)104,1781-812 Probing Excited State Structures and Dynamics of Metal Complexes Using Time-resolved X-rays, Lin X. Chen, Ann. Rev. Phys. Chem. 56, 221-254 (2005). Molecular Structural Dynamics Probed by Ultrafast X-ray Absorption Spectroscopy, C. Bressler and M. Chergui, Annu. Rev. Phys. Chem. (2010) 61: 263-82. Photochemical Processes Revealed by X-ray Transient Absorption Spectroscopy, Lin X. Chen, Xiaoyi Zhang, J. Phys. Chem. Lett. 4, 4000–4013 (2013).
Two-volume book published 2015 • Combines the theory, instrumentation
and applications of x-ray absorption and emission spectroscopies which offer unique diagnostics to study almost any object in the Universe.
• Is the go-to reference book in the subject for all researchers across multi-disciplines since intense beams from modern sources have revolutionized x-ray science in recent years
• Is relevant to students, postdocurates and researchers working on x-rays and related synchrotron sources and applications in materials, physics, medicine, environment/geology, and biomedical materials.
Today’s lecture is based on Chapter 9 of the book entitled “X-ray transient
absorption spectroscopy” by Lin X. Chen
1. Pump-probe spectroscopy
2. Experimental Considerations
2.1 XTA at a Synchrotron Source
2.2 XTA at an X-ray Free Electron Laser Sources
3. Transient Structural Information Investigated by XTA
3.1 Metal center oxidation state
3.2 Electron configuration and orbital energies of X-ray absorbing atoms
3.3 Transient coordination geometry of the metal center
4. X-ray pump-probe absorption spectroscopy, Examples
4.1 Excited state dynamics of transition metal complexes (TMCs)
4.2. Interfacial charge transfer in hybrid systems
4.3 XTA Studies of Metal Center Active Site Structures in Metalloproteins
4.4 XTA using the X-ray Free Electron Lasers
4.5 Other XTA Application Examples
5. Perspective of Pump-probe X-ray spectroscopy
Outline of today’s lecture
1. Pump-probe spectroscopy
Time scales of fundamental dynamic processes
t=0 t1 t2 t3 … tn t∞
Reaction Coordinates
transient states
product
Energy
time
reactant
Scientists’ dream: “Seeing” molecules along the reaction coordinates, and being able to understand and control reaction paths.
Molecular snapshots and reaction control
1. Pump-probe spectroscopy
7
How can we follow a molecule in an ensemble of NA?
Single molecule (by Muybridge) Ensemble of molecules
Molecular snapshots and reaction control 1. Pump-probe spectroscopy
Molecular snapshots and reaction control
Molecular snapshots and reaction control 1. Pump-probe spectroscopy
Molecular snapshots and reaction control
8
t=0 t1 t2 t3 … tn t∞
Reaction Coordinates
laser
pulse
excited
state
transient states
product Probe pulses
Energy
time
reactant
Femtosecond (10-15) laser pulses trigger chemical events synchronously for NA
molecules ensemble, allowing snapshots to be taken.
Photons induce transitions to synchronously generate energetic species, the excited states that then proceed to many different processes. By capturing the optical signatures of transient species, one can follow the reaction kinetics and mechanisms and identify the final products.
S0
S1
S2
SN
T1
Vibration
relaxations
h
exc
itatio
n
fluo
rescen
se
ph
osp
ho
resc
en
se
tf tp
New species
photoinduced processes to be investigated
Discussions: other processes?
1. Pump-probe spectroscopy
1. Pump-probe spectroscopy
Snapshots for molecules: Transient absorption spectroscopy (TA)
460 480 500 520 540 560 580 600 620 640 660
-0.03
-0.02
-0.01
0.00
0.01
0.02
0.03
D A
Time
Wavelength (nm)
Pump
Probe
t
t<0 t=0 t>0
Probe
At one delay time, many pump-probe cycles are collected for sufficient S/N
level in the data;
Changing the delay time step-by-step to cover the entire kinetics trace;
Time resolution determined by the laser pulse duration (i.e., ~10-100 fs);
Time window determined by the optical delay length (i.e. 0-6 ns).
1. Pump-probe spectroscopy
Pump and probe concept
I0 I1
1
0
I
I
tI
tItOD
onpump
offpump
log),(
),(log),(
t
t
1. Pump-probe spectroscopy
Pump and probe concept
1. Pump-probe spectroscopy
Pump excitation light sources
Direct Ti-Sapphire laser output - 800 nm
Harmonic generation - SHG 400 nm and THG 267 nm
Optical parametric amplification - 250-12000 nm
• White light continuum generation
– Advantage: Easy to use and All wavelengths are generated at once
– Disadvantage: Somewhat limited spectral range 330-1000 nm
• Optical parametric amplification
– Advantage: Broad spectral range 250-12000 nm
– Disadvantage: Requires more sophisticated equipment; Only narrow spectrum range can be used – need to scan wavelength.
Laser probe light sources
1. Pump-probe spectroscopy
1. Pump-probe spectroscopy
S0
S1
S2
T1
A
T2
IC
IC TA
F
IC TA
0 100 200 300 400
OD
Probe Delay (ps)
Probe at 540 nm
0 100 200 300 400
O
D
Probe Delay (ps)
Probe at 525 nm
475 500 525 550 575 600 625
0.4 ps
0.6 ps
0.8 ps1.0 ps
1.5 ps
2.5 ps
5 ps
10 ps
20 ps
100 ps
200 ps
400 ps
O
D
Wavelength (nm)
OD UV-vis
Ground state
depletion and
recovery
Excited state
generation
and decay
“Pump” laser pulse:
Single wavelength at a certain absorption feature of the UV-vis spectrum.
“Probe” laser pulse:
White light pulse with a variable optical path to set delay from the “pump” pulse.
Optical transient absorption spectroscopy
2. Experimental Considerations
• Light sources for pump and probe pulses;
• Photon energy differences;
• Timing structure (synchronization of laser with X-ray pulses);
• Samples (absorption coefficients, concentration, lifetimes,
stability);
• Detection scheme
• Capability of optical vs. X-ray transient absorption
spectroscopy
Advanced Photon Source,
Argonne, Illinois. USA
LCLS
APS
Lightsources.org
XFEL
X-ray photon flux evolution in sources 2. Experimental Considerations
Pump excitation light sources
Direct Ti-Sapphire laser output - 800 nm
Harmonic generation - SHG 400 nm and THG 267 nm
Optical parametric amplification - 250-12000 nm
• White light continuum generation
– Advantage: Easy to use and All wavelengths are generated at once
– Disadvantage: Somewhat limited spectral range 330-1000 nm
• Optical parametric amplification
– Advantage: Broad spectral range 250-12000 nm
– Disadvantage: Requires more sophisticated equipment; Only narrow spectrum range can be used – need to scan wavelength.
Laser probe light sources
1. Pump-probe spectroscopy
X-ray probe light sources • Third generation synchrotron sources
• Table top laser driven fs pulsed x-ray pulses
• High harmonic generation
• X-ray free electron lasers
Synchronization of laser pump pulse with x-ray probe pulse through synchrotron RF signal
X-ray signal before the laser pulse X-ray signal change resulted from the laser excitation
0 1 2 3 4
154 ns Δt
Laser pump pulse (t1)
Laser/X-ray Probe pulse (t2)
time
S
Transmission signal (Δt = t2-t1)
Fluorescence signal (Δt = t2-t1)
2. Experimental Considerations
X-ray transient absorption spectroscopy (XTA)
1s
2s, 2p
Valenc
e
Continuum
3s, 3p, 3d, …
EXAFS XANES
4s, 4p, 4d, …
Valence electronic transitions
2. Experimental Considerations
Photon energy difference: visible vs. hard X-ray
Inner shell electronic transitions
21
2. Experimental Considerations
Photon energy difference: visible vs. hard X-ray
22
Laser Pump Pulse
X-ray Probe Pulse
Time
ES2 ES1
APS Standard Operating Mode
Time
154 ns
Time
8.33 ms
Excited state population
120 Hz, <50 fs fwhm
6,500,000 Hz, ~80 ps fwhm Digitizing signals from every x-ray pulse to study structural dynamics on different time scales
LCLS
Beamline 11IDD
2. Experimental Considerations
Timing structures of laser and X-ray pulses
23
Time-resolved x-ray facility at 11IDD
Large scale collaboration with APS
though partner usership and contribute
to general user programs
TOPASNd-YLF Regen Laser w/ SHG & THG
Nd-YLF
Seed Laser
Xe LampMonochromaterPMT
Translation stage
527nm
351nm
470-690 nm
Dref
Dsig
To detection
electronics
sample
CrystalShutter
High Harm.Rej. Mirror
Ion
Chamber
Slits SlitsIon
Chamber
-
Pump
Sample
Laser
Focusing
Lens
Sample circulation
Laser
shutter
Soller slits
Filter ensemble
X-ray from
synchrotron
CrystalShutter
High Harm.Rej. Mirror
Ion
Chamber
Slits SlitsIon
Chamber
CrystalShutterCrystalShutterCrystalShutter
High Harm.Rej. MirrorHigh Harm.Rej. Mirror
Ion
Chamber
Ion
Chamber
SlitsSlits SlitsSlitsIon
Chamber
Ion
Chamber
-
PumpPump
X-ray Hutch
Q-switch control
Storage RingEvolution272 kHz Shutter
control
Pulse
DelayGenerator
PulseDelayGenerator
PhotodiodeLaser pulseSignal 1kHz
CrystalShutter
High Harm.Rej. Mirror
Ion
Chamber
Slits SlitsIon
Chamber
-
Pump
Sample
Laser
Focusing
Lens
Sample circulation
Laser
shutter
Soller slits
Filter ensemble
X-ray from
synchrotron
CrystalShutter
High Harm.Rej. Mirror
Ion
Chamber
Slits SlitsIon
Chamber
CrystalShutterCrystalShutterCrystalShutter
High Harm.Rej. MirrorHigh Harm.Rej. Mirror
Ion
Chamber
Ion
Chamber
SlitsSlits SlitsSlitsIon
Chamber
Ion
Chamber
PumpPump
Sample
Laser
Focusing
Lens
Sample circulation
Laser
shutter
Soller slits
Filter ensemble
X-ray from
synchrotron
Laser Room
X-ray Hutch
Q-switch control
Storage RingEvolution272 kHz Shutter
control
Pulse
DelayGenerator
PulseDelayGenerator
PhotodiodeLaser pulseSignal 1kHz
Pilatus
X-ray fluo.
detector
Fast
Digitizer
To
computer
-
Xe LampMonochromaterPMT
Translation stage470-
Dref
Dsig
To detection
electronics
RF/4 88MHz
for mode-lock
driver
sample
OPA
RF/4 88MHz
for mode-lock
driver
Amplifier laser
TOPASNd-YLF Regen Laser w/ SHG & THG
Nd-YLF
Seed Laser
Xe LampMonochromaterPMT
Translation stage
527nm
351nm
470-690 nm
Dref
Dsig
To detection
electronics
sample
CrystalShutter
High Harm.Rej. Mirror
Ion
Chamber
Slits SlitsIon
Chamber
CrystalShutterCrystalShutterCrystalShutter
High Harm.Rej. MirrorHigh Harm.Rej. Mirror
Ion
Chamber
Ion
Chamber
SlitsSlits SlitsSlitsIon
Chamber
Ion
Chamber
-
PumpPump
Sample
Laser
Focusing
Lens
Sample circulation
Laser
shutter
Soller slits
Filter ensemble
X-ray from
synchrotron
CrystalShutterCrystalShutterCrystalShutter
High Harm.Rej. MirrorHigh Harm.Rej. Mirror
Ion
Chamber
Ion
Chamber
SlitsSlits SlitsSlitsIon
Chamber
Ion
Chamber
CrystalShutterCrystalShutterCrystalShutterCrystalShutter
High Harm.Rej. MirrorHigh Harm.Rej. Mirror
Ion
Chamber
Ion
Chamber
SlitsSlits SlitsSlitsIon
Chamber
Ion
Chamber
-
PumpPump
X-ray Hutch
Q-switch control
Storage RingEvolution272 kHz Shutter
control
Pulse
DelayGenerator
PulseDelayGenerator
PhotodiodeLaser pulseSignal 1kHz
CrystalShutter
High Harm.Rej. Mirror
Ion
Chamber
Slits SlitsIon
Chamber
CrystalShutterCrystalShutterCrystalShutter
High Harm.Rej. MirrorHigh Harm.Rej. Mirror
Ion
Chamber
Ion
Chamber
SlitsSlits SlitsSlitsIon
Chamber
Ion
Chamber
-
PumpPump
Sample
Laser
Focusing
Lens
Sample circulation
Laser
shutter
Soller slits
Filter ensemble
X-ray from
synchrotron
CrystalShutterCrystalShutterCrystalShutter
High Harm.Rej. MirrorHigh Harm.Rej. Mirror
Ion
Chamber
Ion
Chamber
SlitsSlits SlitsSlitsIon
Chamber
Ion
Chamber
CrystalShutterCrystalShutterCrystalShutterCrystalShutter
High Harm.Rej. MirrorHigh Harm.Rej. Mirror
Ion
Chamber
Ion
Chamber
SlitsSlits SlitsSlitsIon
Chamber
Ion
Chamber
PumpPump
Sample
Laser
Focusing
Lens
Sample circulation
Laser
shutter
Soller slits
Filter ensemble
X-ray from
synchrotron
Laser Room
X-ray Hutch
Q-switch control
Storage RingEvolution272 kHz Shutter
control
Pulse
DelayGenerator
PulseDelayGenerator
PhotodiodeLaser pulseSignal 1kHz
Pilatus
X-ray fluo.
detector
Fast
Digitizer
To
computer
-
Xe LampMonochromaterPMT
Translation stage470-
Dref
Dsig
To detection
electronics
RF/4 88MHz
for mode-lock
driver
sample
OPA
RF/4 88MHz
for mode-lock
driver
Amplifier laser
2. Experimental Considerations
Synchrotronization of laser pulses with X-ray pulses at the APS
24
2. Experimental Considerations
Sample requirements
• Lifetime of the transient structure > x-ray pulse duration (e.g. 100 ps) and less the x-ray pulse separation;
• Absorption coefficient or extinction coefficient at the excitation laser wavelength sufficiently high to ensure effective excitation;
• Concentration of the x-ray absorbing atoms sufficiently high for either transmission or fluorescence detection;
• Stability of the sample sufficiently high under illumination of the laser and x-ray pulses;
• Sample quantity sufficiently large to unsure necessary refresh of the sample during the data acquisition period;
• Meaningful samples.
2. Experimental Considerations
Time
X-ray Pulse Train 3.68 μs
For example, the pump-probe cycle repeats at 1 kHz due to the laser pulse repetition rate resulting in a factor of ~1,700 or 6,500 reduction of the x-ray photon flux! Solutions: Higher x-ray flux, higher repetition rate of laser.
16mA 84mA
(271kHz)
Laser Pulse Train 1 ms
Time
(1kHz)
Time
153 ns
4mA
(6504kHz)
Hybrid mode
24-bunch mode
Sample requirements: X-ray and laser pulse repetition rates
26
2. Experimental Considerations
Sample requirements: The ground state absorption of laser photons
0.1
0.2
0.3
0.4
0.5
0.60.7
0.80.9
2 4 6 8 10 12 14 16 18 200.0
0.2
0.4
0.6
0.8
1.0
B
=20,000M-1cm
-1
Concentration (mM)
Pu
mp P
uls
e E
nerg
y (
mJ)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
0.10.2
0.30.4
0.5
0.6
0.7
0.8
0 2000 4000 6000 8000 100000.0
0.2
0.4
0.6
0.8
1.0
C=2mM A
(M-1cm
-1)
Pu
mp
Pu
lse
En
erg
y (
mJ)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
fP e Q
N hex
ktlC f Q eex
kt
[ ]( ) ( )1 10 1
P, laser pulse energy (J); k, rate const., (s-1); t, time, s; ε (λ), absorption coeff. at laser wavelength λ (M-1cm-1); l, thickness (cm); C, concentration (M); N, total number of molecules illuminated by the laser.
350 400 450 500 550 600 6500.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
434
414
OD
wavelength (nm)
toluene
25% pyridine (v)
50% pyridine (v)
75% pyridine (v)
pyridine
X10
601
563
527
X-ray
Sample requirements: X-ray and laser photon absorption cross section
2. Experimental Considerations
2. Experimental Considerations
Laser
Sample requirements: X-ray and laser photon absorption cross section
2. Experimental Considerations
Laser+
X-ray
Sample requirements: X-ray and laser photon absorption cross section
2. Experimental Considerations
Laser+
X-ray
0 5 10 15 20
1
10
100
1000
Ab
so
rptio
n (
cm
-1)
[Zn(II)] (mM)
Laser 2.21 eV (560 nm)
X-ray 10,000 eV
Sample requirements: X-ray and laser photon absorption cross section
2. Experimental Considerations
fP e Q
N hex
ktlC f Q eex
kt
[ ]( ) ( )1 10 1
Extracting excited state (or transient state) spectrum from XTA
P, laser pulse energy (J);
k, rate const., (s-1);
t, time, s;
ε (λ), absorption coeff. at laser wavelength λ (M-1cm-1);
l, thickness (cm);
C, concentration (M);
N, total number of molecules illuminated by the laser.
)],(),()[(),(
),()(),()]([
),()(),()(),(
tktktftk
tktftktf
tktftktftk
GSESESGS
ESESGSES
ESESGSGS
1
Two unknowns and one equation → need to find fES via other means
A, via calculation
2. Experimental Considerations
)}()()]()[({(
)(log
)}(),()()]()[,()({(
),(log
)],()(),()([(
),()(log),(
tftf
tfCtfC
C
tCtC
CtOD
ESESESGS
GS
ESGSESESGSGS
GSGS
ESESGSGS
GSGS
1
010
0
0
From laser pump, laser probe transient absorption spectroscopy in a two-state
example, where the total concentration of excited and ground states remain to be
the starting ground state concentration CGS(λ,t=0):
If the extinction coefficient for the excited state at a particular detection
wavelength λ, εES(λ) = 0,
OD
ES
OD
ES
ES
ESESGS
GS
etfetf
tftftf
tOD
11
11
1
1
)()]([
)](log[)]([
log)]()[((
)(log),(
B. via optical transient absorption (e.g. two state system)
Extracting excited state (or transient state) spectrum from XTA
2. Experimental Considerations
C. via calculation (one example by Grigory Smolentsev et al.)
Smolentsev, G.; Soldatov, A. Journal of Synchrotron Radiation 2006, 13, 19-29.
Smolentsev, G.; Soldatov, A. V. Computational Materials Science 2007, 39, 569-574.
Extracting excited state (or transient state) spectrum from XTA
2. Experimental Considerations
Slits
Ion Chamber Detector 1
X-ray Beam
High Harmonic Rejection Mirror Slits
Ion Chamber Detector 1
To fast digitizer
To fast digitizer
S
Fast Digitizer
Electronic Delay
Generator
Q-switch Control
Hybrid Pixel 2D Detector
for XRD
Seed Laser
Amplifier Laser and OPA
271 kHz Ring Evolution Signal
RF/4 88MHz
To Computer Electronic
Delay Generato
r
Photodiode
Detection and sample delivery
Pump laser pulse (on/off) ΔOD(t)
OTA:
• How fast molecule moves; • How to get from R → P; • How energy flows; • Transient species population; • Correlation of electronic transitions; • How molecular movements affect functions.
XTA (New):
• Electronic configuration; • Geometry; • Oxidation states • Molecular orbital energies; • Transient species lifetime; • Correlations of electronic transition with nuclear movements.
Pump: creates changes or triggers reactions Probe: interrogates changes
Sample
Molecular snapshots and reaction control 3. Transient Structural Information Investigated by XTA
Metal center oxidation state in the excited state
3. Transient Structural Information Investigated by XTA
Jahn-Teller
Distortion
hν
Franck-Condon
State
MLCT
State—
“Flattened”
kr
Cu(I)
Cu(II)*
Cu(II)*
kr’+knr”
Cu(I)
knr’
Strongly
Interacting
< 2 ns
Weakly
Interacting
> 100 ns
Ground
State
Cu(II)*
MLCT State—
Solvent
Complex<0.1 ps
<20 psJahn-Teller
Distortion
hν
Franck-Condon
State
MLCT
State—
“Flattened”
kr
Cu(I)
Cu(II)*
Cu(II)*
kr’+knr”
Cu(I)
knr’
Strongly
Interacting
< 2 ns
Weakly
Interacting
> 100 ns
Ground
State
Cu(II)*
MLCT State—
Solvent
Complex<0.1 ps
<20 ps
JACS 129, 2147 (2007), 125, 7022 (2003), 124, 10861 (2002).
1s to 4pz
Cu(I)→Cu(II) 1s to 3d
[CuI(dmp)2]+
Electron configuration and orbital energies of X-ray absorbing atoms
3. Transient Structural Information Investigated by XTA
7.11 7.12 7.13 7.14 7.15
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Fe(III)Mb
Fe(II)CO-Mb
Fe(II)-Mb after CO
photodissociation
Norm
aliz
ed
(E)
Energy (keV)
7.108 7.112 7.116
MbFe(II)CO MbFe(II)*
3d
hv, -CO
1s
2231yx
ds
231z
ds
Photodissociation of CO from heme in myoglobin
Stickrath et al., J. Phys. Chem. A. 117, 4705 - 4712 (2013)
Transient coordination geometry of the metal center 3. Transient Structural Information Investigated by XTA
Fe(II)CO-Mb CN R(Å) σ2(Å2) ∆E(eV) Fe(II)Mb CN R(Å) σ2(Å2) ∆E(eV)
Fe-C(O) 1 1.76 0.0001 18.10 16.47
Fe-N(His,Heme) 5 1.99 0.0013 5 2.05 0.0042
Fe-O(CO) 1 2.84 0.0002
Fe-C(CNC) 10 3.08 0.0080 10 3.05 0.0034
Fe-C 4 3.38 0.0001 4 3.47 0.0010
Fe-C 10 4.41 0.0001 9 4.21 0.0023
Table 1. Iron heme structural parameters (Residual = 8.11, S2= 0.9)
Photodissociation of CO from heme in myoglobin
Stickrath et al.,
J. Phys. Chem.
A. 117, 4705 -
4712 (2013)
Metal Ligand MLn
MLCT
LMCT
np
ns
(n-1)d
π*
π
σ
E
Cu(dmp)2+
The metal-to-ligand-charge-transfer (MLCT) states
MLCT transitions are often origins for transition metal complexes to be used
in solar energy conversion initiated by electron density shifts between the
metal and the ligands. Examples are DSSC, photocatalysis, etc.
4. XTA spectroscopy, Examples
Excited state structural dynamics of Cu(I) diimine complexes
40
[CuI(dmp)2]+ → [CuII(dmp-)(dmp)]2++ e-
[RuII(bpy)3]2+ → [RuIII(bpy-)(bpy)2]3++ e-
D2d D2
τ1 τ2,τ3
τ4
τ5
τ6
τ1- 1MLCT formation; τ2- J-T distortion, 0.3-0.6 ps; τ3- ISC, 1-20 ps; τ4,
3MLCT “ligation” > 100 ps?;
Τ5,6 3MLCT decay, 1ns to 3µs.
Two key structural factors: • Orientation of two ligand planes: ISC • Solvent accessibility to the Cu* center – electron density transfer
from “ligating” solvent to 3d, 3MLCT lifetime.
McMillin, Sauvage,
Karpishin, Meyer,
Castellano, Chen, Tahara,
Iwamura, Penfold, …
Mara, Fransted, Chen,
Coord. Chem. Rev.,
282, 2-18 (2015).
4. XTA spectroscopy, Examples
4. XTA spectroscopy, Examples
Excited state structural dynamics of Cu(I) diimine complexes
8.97 8.98 8.99 9.00 9.01 9.02
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
(E
) (n
orm
alize
d)
Energy (keV)
[Cu(I)dmp2]+
Excited State
[Cu(II)dmp2]2+
τ1= 0.6 ps τ1= N/A τ2= 13 ps τ2= 13 ps τ3= 1.6/100 ns τ3= 100/N/A ns
Transient Cu(II) in [CuI(dmp)2]+ MLCT state: 3d hole remains – transient “ligation” and no formal bond forms with the solvent, but only direct access of the solvent to the Cu(II)* center could shorten the MLCT lifetime in coordinating solvent; Cu(II) in [CuII(dmp)2]2+ : 3d hole filled due to the ligation.16
41
8.97 8.98 8.99 9.00 9.01 9.02
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Ab
so
rptio
n (
no
rma
lize
d)
Energy (eV)
Cu(I)(dppS)2
Excited State
Cu(II)(dppS)2
8.976 8.980 8.984-0.010.000.010.020.030.040.050.060.070.080.090.10
(J.-P. Sauvage and coworkers)
8.976 8.978 8.980 8.9820.00
0.05
0.10
0.15
Cu K-edge XANES
1s to 4pz
1s to 3d
Cu(I)→Cu(II)
1s to 3d
1s to 3d
[CuI(dmp)2]+ [CuI(dppS)2]+
[CuI(dmp)2]+ [CuI(dppS)2]+
4. XTA spectroscopy, Examples
Excited state structural dynamics of Cu(I) diimine complexes
2 4 6 8 10 12-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5 Ground State
Excited State
(k
)k2
k(Angstrom-1)
(k) N F (k)e e
kr k
krj j
2 k
2r
k j ij
jj
2 2
j
j
( ) sin( ( ))2
2
0 1 2 3 40.00
0.02
0.04
0.06
0.08
0.10
FT
[(k
)k2]
R (before phase correction, Angstrom)
Ground State
Excited State
FT
Cu-N
Cu-C
Removal of
antibonding 3d
electron→bond
shortening
Transient exciplex forms when the space and the MLCT state lifetime allow, but not necessarily forms a normal bond between Cu(II) and solvent.
EXAFS of the MLCT State of [CuI(dmp)2]+
4. XTA spectroscopy, Examples
Excited state structural dynamics of Cu(I) diimine complexes
Mara, Coskun, Dimitrijevic, Barin, Kokhan, Stickrath, Ruppert, Tiede, Stoddart, Sauvage, Chen, Angew. Chem. Intl. Ed. 51, 12711–12715 (2012).
232
2IIk
2II OTi](dppS)[CuTiO*(dppS)](dppS)[Cu TE
2s
13.7 ps
100 ns
0.5V
-1.57V
3MLCT
1MLCT
4. XTA spectroscopy, Examples
Excited state structural dynamics of Cu(I) diimine complexes 8980 9000 9020
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Energy (eV)
Abso
rptio
n (
no
rma
lize
d)
Energy (eV)
4
4* - 100 ps
8980 9000 9020
4-TiO2
4*-TiO2 - 100 ps
A B
C D
0 2 4 6 8 10 12 14 100 1000
0.0
0.2
0.4
0.6
0.8
1.0
Ab
sorp
tion
(n
orm
aliz
ed
)
Time (ps)
4
4-TiO2
In solution On TiO2
• ~40% injection yield, due to charge recombination; • Linker length independent; • Electron transfer mechanism and pathway: through
bond; • Future design aims at minimize charge recombination.
1s →4pz
MLCT state decay by OTA Mara, Coskun, Dimitrijevic, Barin, Kokhan, Stickrath, Ruppert, Tiede, Stoddart, Sauvage, Chen, Angew. Chem. Intl. Ed. 51, 12711–12715 (2012).
Excited states of metalloporphyrins: electron donors or acceptors, light harvesting pigments, photocatalysis, functional site of heme proteins, photovoltaic materials.
Moore et al.
NN
NNM
Myoglobin
Photosynthetic bacterial reaction center protein
++++
Photosynthetic bacterial light harvesting protein
Metalloporphyrins
FeIII
FeIII
FeII
FeII
O
FeII
FeIV
FeII
FeIII
O∙
1/2O2 hv(λLMCT
)
τspring<200ps
S
(O)S
O
Photocatalyst
4. XTA spectroscopy, Examples
Capturing a Photoexcited Molecular Structure Through Time-Domain X-ray
Absorption Fine Structure, L. X. Chen, W. J. H. Jäger, G. Jennings, D. J.
Gosztola, A. Munkholm, J. P. Hessler, Science, 292, 262-264(2001).
• (π,π*)→(d,d,) conversion mechanism; • Multiple electron shift steps but
sequence is unclear; • Influence of excited state structures on
MO energy levels; • Role of the solvent and ligation; • Transient oxidation state of Ni.
3dxz 3dyz
3dxy
3dz2
3dx2-y2
Ni(II) 3d8
Square-planar
π*
π
Porphyrin Ni
8.32 8.34 8.36 8.38 8.40
0.0
0.2
0.4
0.6
0.8
1.0
1.2
[(E
)-
0(E
)]/
0(E
)
Energy (keV)
"t=100 ps" laser-off
"t=100 ps" Excited state
Chen et al., JACS (2007)
1s → 4pz
1s →3d
(LCLS study)
(APS study)
APS results
4. XTA spectroscopy, Examples
8328 8329 8330 8331 8332 8333 8334 8335 8336
No laser
t = "0" ps
t = "100" ps
T1
S0
(E
)
Energy (eV)
3dx2-y2
3dz2
• Ni-N and Ni-Cα distances increase in the T1 state due to the reduction of the bond order when the excitation adds electron to antibonding MO.
• The effective radius of Ni(II) is larger and fits porphyrin cavity better, and hence the macrocycle is flatter than in the ground state.
4. XTA spectroscopy, Examples
APS: JACS (2007),
Chem. Sci. (2010).
8330 8332 8334
1s -> 3dz2
1s -> 3dx2-y2
Laser 527 nm
No laser
(E
)
Energy (eV)LCLS exp. Shelby et al., J. Am. Chem. Soc. 138, 8752–8764 (2016)
4. XTA spectroscopy, Examples
XTA at X-ray free electron laser source
1s → 4pz
1s →3d
• A new transient feature in 1-2 ps detected: Ni(I)?;
• To be confirmed by calculations about the existence of Ni(I) T’ state.
Shelby et al., J. Am. Chem. Soc. 138, 8752–8764 (2016)
• LCLS X-ray pulse: ~50 fs (fwhm), 1012photons/pulse, 103-4 x higher than pump-probe exp. at synchrotrons;
• Self-amplified-spontaneous emission (SASE) with ~50 eV energy range, XANES spectra only.
Lemke et al., J. Phys. Chem. A,
117, 735 (2013)
4. XTA spectroscopy, Examples
XTA at X-ray free electron laser source
GS depletion
T1 rise T’* Ni(I)? rise and decay
( GSddTTSk
yxz
kk
3222
21 )3,3(*'*),( 11 (1 ps)-1 (0.3 ps)-1 (>200 ps)-1
Inverted kinetics )()(),(3
0
tPEAtEAi
iitotal
4. XTA spectroscopy, Examples
XTA at X-ray free electron laser source
Orbital energies and changes in various excited states (Xiaosong Li)
Exp
Calculation
1s →4pz 1s →3d
3dxz 3dyz
3dxy
3dz2
3dx2-y2
π*
π
Porphyrin Ni
Inputs for excited-state XAS modeling
Wavefunc. S0 S1(π, π*) T’ T(d,d) S0 S0 T(d,d) T(d,d)
Geometry S0 S1(π,π*) T’ T(d,d) T’ T(d,d) S0 S1
Calculated Ni orbital energies (eV)
1s α -8167.47 -0.05 2.02 -1.17 0.37 -0.34 -0.67 -0.61
1s β -8167.47 -0.05 2.03 -1.17 0.37 -0.34 -0.67 -0.61
4pz α 1.39 -0.07 0.18 -0.23 0.06 -0.03 -0.15 -0.16
4pz β 1.39 -0.06 0.05 -0.44 0.06 -0.03 -0.34 -0.34
Energy-specific TDDFT (ES-TDDFT) using the PBE1PBE and Ahlrichs' def2-TZVP basis set with diffuse functions on the nickel atom
S0
T1
T’*
4. XTA spectroscopy, Examples
XTA at X-ray free electron laser source
A wide range of transient structures during photochemical reactions have been captured by high quality XTA studies which become routine and sample property dependent;
Capturing transition state in chemical reactions by fs x-ray pulses is still a significant challenge and will bring new insight into matter interactions with which requires X-ray free electron lasers with stable timing and spectral tunability;
Computational and theoretical works are urgently needed to model photochemical pathways through unrelaxed excited states, excited state coherence, initial reaction conditions and core/valence excitations.
Simultaneously obtaining the structural dynamics on the initial and stepwise catalytic reactions remain to be challenging.
5. Perspective of X-ray Transient Absorption Spectroscopy